DE1257093B - Process for dyeing and printing fiber material made from aromatic polyesters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN WIW PATENT OFFICE

EDITORIAL

Int. CL:

D06p

German class: 8 m-1/01

'OS

Number: 1 257 093

File number: C 25580IV c / 8 m

Filing date: November 22, 1961

Open date: December 28, 1967

It has been found that valuable dyeings and prints on fiber material made of aromatic polyesters, in particular polyethylene glycol terephthalates, can be obtained when used as dyes of acidic, water-solubilizing groups free, at most used anthraquinones containing four fused rings that have an arylsulfonylamino group have, with the exception of the dyes used according to Patent 1,162,805.

The anthraquinones to be used according to the invention preferably contain the arylsulfonylamino group in the α-position and in addition to the group mentioned, it is expedient to have at least one auxochrome. Amino, hydroxyl, alkoxy, alkyl mercapto groups or halogen atoms are used as auxochromes called. The auxochrome can also be a member of a fused-on hetero ring, such as in the isothioazole anthrone. Arylsulfonyl radicals are, for example, the radicals of the 1- or 2-NaphthaIinsulfonsäure, but especially benzenesulfonic acid or their in the benzene nucleus, for example by halogen atoms, hydroxyl, low molecular weight Alkoxy or alkyl group substituted derivatives mentioned.

Dyes of the formula q χ are of particular interest

NH-SO ₂

a

wherein X is an amino or hydroxyl group, Y is a hydrogen or halogen atom or an alkyl mercapto group and Z represents a hydrogen or halogen atom, a hydroxyl group, an alkyl or alkoxy group means. The alkyl and alkoxy groups preferably contain at most 6 carbon atoms and can also contain substituents, for example hydroxyl or alkoxy groups.

The following are examples of the dyes to be used according to the invention:

1-p-toluenesulfonylaminoanthraquinone, l-ChloM-p-toluenesulfonylaminoanthraquinone, l-hydroxy-4-p-toluenesulfonylarninoanthra-

chinone,
M-dihydroxy-Sp-toluenesulfonylaminoanthraquinone,

l-methoxy-4-p-toluenesulfonylaminoanthraquinone,

Process for dyeing and printing fiber material made from aromatic polyesters

Applicant:

CIBA Aktiengesellschaft, Basel (Switzerland)

Representative:

Dr.-Ing. Dr. jur. F. Redies,

Dr. rer. nat. B. Redies, Dr. rer. nat. D. Türk and Dipl.-Ing. Ch. Gille, patent attorneys, Düsseldorf-Benrath 3, Erich-Ollenhauer-Str. 7th

Named as inventor:

Dr. Hans Rudolf Rickenbacher, Basel; Dr. Paul Grossmann, Binningen (Switzerland)

Claimed priority:

Switzerland of 23 November 1960 (13 148)

l-amino-4-p-toluenesulfonylaminoanthraquinone, l-methylamino-4-benzenesulfonylaminoanthra-

chinone,
l-phenylamino-4-benzenesulfonylaminoanthra-

chinone,
l-amino ^ -methoxy ^ -ß-naphthalenesulfonyl-

aminoanthraquinone,
l-amino-2 - (/ J-hydroxyethoxy) -4-p-toluene-

sulfonylaminoanthraquinone, 4- or S-benzenesulfonylamino-l ^ -isothiazolanthrone.

Some of the dyes mentioned are known compounds which, according to known processes, for example by reacting the corresponding amino compound with an aryl sulfonic acid chloride, or by condensation of a u-haloanthraquinone be obtained with an aryl sulfonic acid amide.

Instead of the pure dyes, it is also possible to use mixtures of dyes, for example mixtures of two of the dyes to be used according to the invention, which are distinguished by the substituents differentiate in the benzenesulfonyl radical. Such mixtures often show up against the individual dyes an improved drawing ability.

709 710/558

For dyeing, the dyes mentioned are advantageously used in finely divided form and dyed with the addition of dispersants such as soap, sulphite cellulose waste liquor or synthetic detergents, or a combination of different wetting and dispersing agents. As a rule, it is useful to convert the dyes to be used into a dye preparation before dyeing, the one Contains dispersant and finely divided dye in such a form that when the to Dye preparations with water create a fine dispersion. Such dye preparations can be used in known Way, e.g. B. by falling over of the dye from sulfuric acid and grinding the so obtained slurry with sulphite waste liquor, optionally also by grinding the dye in highly efficient grinding devices in dry or wet form with or without the addition of dispersants during the grinding process.

To achieve stronger dyeings on polyethylene glycol terephthalate fibers, it has proven to be expedient to add a swelling agent to the dye bath or, in particular, to dye the dyeing process under pressure at temperatures above 100 ° C., for example at .12OC. perform. Suitable swelling agents are aromatic carboxylic acids, for example benzoic acid or salicylic acid, phenols such as o- or p-hydroxydiphenyl, aromatic halogen compounds, for example chlorobenzene, o-dichlorobenzene or trichlorobenzene, phenylmethylcarbinol or diphenyl. When dyeing under pressure, it is advantageous to make the dyebath slightly acidic, for example by adding a weak acid, e.g. B. acetic acid.

The dyes to be used according to the invention are also suitable thanks to their alkalinity for dyeing according to the so-called thermal process, after which the fabric to be dyed with an aqueous dispersion of the dye, which is appropriate 1 to 50% urea and a thickener, in particular sodium alginate, preferably at temperatures of at most 60 ° C impregnated and squeezed off as usual. It is advisable to squeeze in such a way that the impregnated Goods 50 to 100% of their initial weight of dye liquid holding back.

To fix the dye, the fabric impregnated in this way is expediently after Drying, e.g. B. in a warm air stream, to temperatures of over 100 ° C, for example zwisehen 180 to 210 ° C, heated.

The heat setting process just mentioned is of particular interest for dyeing blended fabrics made of polyester fibers and cellulose fibers, especially cotton. In this case contains the padding liquid, in addition to the dyes to be used according to the invention, for dyeing dyes suitable for cotton, especially vat dyes, or so-called reactive dyes, d. H. Dyes on the cellulose fiber under f> ° Formation of a chemical bond are fixable, so for example dyes containing a Chlorotriazine or chlordiazine residue. In the latter In this case, it proves to be expedient to add an acid-binding agent to the padding solution, for example a Add alkali carbonate or alkali phosphate, alkali borate or perborate or mixtures thereof. at The use of vat dyes is a treatment of the padded fabric after the hit / .c treatment with an aqueous alkaline solution of a reducing agent commonly used in kip dyeing necessary.

The dyeings obtained according to the process according to the invention are expediently one Subjected aftertreatment, for example by heating with an aqueous solution of an ion-free egg. Detergent.

Instead of by impregnation, the specified dyes can be used according to the method according to the invention can also be applied by printing. For this purpose one uses z. B. a printing ink, in addition to the aids commonly used in printing, such as wetting agents and thickeners, the finely pergated dye, optionally in a mixture with one of the above-mentioned cotton dyes, optionally in the presence of urea and / or an acid-binding agent.

The process according to the invention gives strong, full colorations and prints of excellent wet fastness properties and especially excellent light and sublimation fastness.

Compared to that in the USA. - Patent 2,757,064 used to dye polyesters 1,4-diamino-2,3-dichloroanthraquinone and the in the German Auslegeschrift 1080 063 used l-amino-2-methoxy-4-hydroxyanthraquinone for dyeing polyesters show the closest comparable dyes to be used according to the invention the advantage of better fastness to sublimation.

In the following examples, unless otherwise stated, the parts mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

example 1

1 part of an aqueous paste of the dye of the formula is ground

O NHSO, -

with about a part of dried sulphite cellulose waste liquor in a roller mill to a fine dough with a dye content of 10%.

100 parts Polyälhylcnglykollerephthalat - fiber material are in a bath, which to 1000 parts Water 1 to 2 parts of the sodium salt of N-benzyl-μ-heptadecyl-benzimidazole disulfonic acid and contains 1 part concentrated aqueous ammonia solution, pre-cleaned for half an hour. Afterward the material is placed in a dyebath of 3000 parts of water in which the according to Paragraph 1 obtained dye paste with the addition of 4 parts of the sodium salt of N-benzyl- '. I-heptadecylbenzimidazole-disulfonic acid was dispersed. The whole thing is heated to 120 ° in a pressure vessel and kept at this temperature for about 1/2 hour. It is then rinsed well and, if necessary, with a solution made up of 1000 parts of water

1 part of the sodium salt of N-benzyl-n-hcptadecylbenzimidazole-disulfonic acid contains, washed for half an hour at 60 to 80 °. You get one pure pink color with excellent sublimation and lightfastness.

The good drawability of this dye on Polyester fibers are surprising because the 1-amino-2-alkoxy-4-benzoylaminoanthraquinones according to the German Auslegeschrift 1039161 as pigment dyes are used, which are known to have no drawability on synthetic fibers.

The table below lists a number of other dyes that, after the im Paragraph 1 specified process dyed, polyethylene glycol crephthalate fibers dye in the shades given in column TI.

Color of excellent sublimation and lightness.

Il

Example 3

One mixes

I)

IO

15 300 parts of gum arabic (1
300 parts crystal rubber (1: 2)
250 parts of water
40 parts of cyclohexanone
40 parts of thiodiglycol

50 parts of a I0 ^u / o solution of the sodium salt of m-Nitrobcnzolsulfonsäure
20 parts of a mixture of potassium oleate and pine oil

1000 parts

1 1 -Benzolsulfonylamino- greenish yellow

anthraquinone

1-chloro-4-benzenesulfonyl yellow

aminoanthraquinone

1-Amino-2- (ß-hydroxyethoxy) - pink
4-p-toluenesulfonylaminoanlhraquinone

1-Amino-2-methylmcrcapto- red violet
4-p-toluenesulfonylaminoanthraquinone!

5 L-anilino-4-p-toluenesulfonyl blue-violet
aminoanthraquinone

5-benzenesulfony) amino-l, 9-iso- ■ reddish yellow
thiazolanthrone

5-p-Toluenesulfonylamino-Rotstichigclb

1,9-isothiazole anthrone

1 -Amino ^ -hydroxy-Sp-toluene- bluish-tinted red
sulfonamidoanthraquinone

1 -Benzoylamino-8-p-toluene yellow
sulfonamidoanthraquinone

With the aid of a high-speed stirrer, 200 parts of the dyestuff paste obtained in accordance with Example 1, paragraph 1, are stirred into 800 parts of this thickened stock until it is completely dispersed. Polyethylene glycol terephthalate fabric is printed with this paste. After printing, the fabric is dried and ^{steamed for 45 minutes at: t} / i atü, rinsed in cold water for 10 minutes, spun off and dried. A true pink color is obtained.

Example 4

200 parts of urea and 20 parts of the red dye of the formula are dissolved in 400 parts of water

HO NHCOCM ₂ CH ₂ Cl

35

NaO ₃ S

40 SO, Na

Example 2

100 parts of polyethylene glycol terephthalate fiber material are pre-cleaned for half an hour in a bath containing 1 to 2 parts of the sodium salt of N-benzyl-μ-heptadecylbenzimidazole disulfonic acid and 1 part of concentrated aqueous ammonia solution per 1000 parts of water. The material is then pre-swollen for half an hour at 80 "in a dyebath which contains, in 300 parts of water, 15 parts of a mixture of approximately equal parts of o-hydroxydiphenyl, pine oil and Turkish red oil and 15 parts of acetic acid Bad ^50: cool and adds to according to example 1, paragraph 1, Farbsloffteig obtained is bringing the bathroom in V> to _^3/4 hours cooking and stained for 1 to 1 '/ ·> hours as close to Kochlempcratur then.. is rinsed well and, if necessary, washed with a solution which contains 1 part of the sodium salt of N-benzyl - ^ - heptadecylbenzimidazole-disulphonic acid per 1000 parts of water for half an hour at 60 to 80 ^: A pinkish-red color is obtained by boiling. 100 parts are poured into this solution an aqueous dispersion containing 30 parts of l-amino-2-methoxy-4-p-toluenesulfonamidanthraquinone and 2 parts of the sodium salt of diisobutylnaphthalenesulfonic acid, mixed in on a high-speed stirrer minutes, 100 parts of a 20% sodium carbonate solution and 400 parts of a 5% sodium alginate solution are added at the same time.

With the pad solution thus obtained, a mixed fabric of 35 parts of cotton becomes at 50 to 60 " and 65 parts of polyethylene glycol terephthalate padded that the impregnated goods 65 to 70% of their Retains initial weight of dye solution, dried and then for one minute subjected to a heat treatment at 200 to 210 °. Then for 20 minutes in a Solution containing 2 g / l of an ion-free detergent and 2 g / l calcined sodium carbonate Washed boiling temperature, rinsed and dried. A pure pink color of very good color is obtained Authenticity properties.

Claims (5)

Patent claims: 1. Process for dyeing and printing fiber material made from aromatic polyesters, in particular Polyethylene glycol terephthalate, characterized by that as Anthraquinones containing at most four condensed rings are used, which are produced by acidic, water-solubilizing groups are free and contain an arylsulfonylamino group, whereby the dyes used according to patent 1,162,805 are excluded. 2. The method according to claim 1, characterized in that one uses anthraquinones, which contain the arylsulfonylamino group in an a-position. 3. Process according to Claims 1 and 2, characterized in that one anthraquinones used, which in addition to the arylsulfonylamino group also contain at least one auxochrome. 4. Process according to Claims 1 to 3, characterized in that one anthraquinones used, which contain a phenylsulfonylamino group as arylsulfonylamino group. 5. The method according to claims 1 to 4, characterized in that one color substances of the formula
O O NHSO used, in which X is an amino or hydroxyl group, Y is a hydrogen or halogen atom or an alkyl mercapto group and Z is a hydrogen or halogen atom, a hydroxyl group or a low molecular weight alkyl or alkoxy group. Considered publications:
German Auslegeschrift No. 1,061,284;
U.S. Patent No. 2,757,064. Legacy Patents Considered:
German Patent No. 1 162 805. When the registration is announced, there is a staining table with explanations and a Priority document has been laid out. 709 710/558 12.67 © Bundesdruckerei Berlin